CN112725660A - Powder metallurgy preparation method of graphene reinforced aluminum-based composite material - Google Patents
Powder metallurgy preparation method of graphene reinforced aluminum-based composite material Download PDFInfo
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- B22F2302/40—Carbon, graphite
Abstract
The invention provides a powder metallurgy preparation method of a graphene reinforced aluminum-based composite material. The matrix powder and the graphene are uniformly compounded by long-time low-energy ball milling, and meanwhile, the occurrence of interface reaction can be avoided, so that the complete structure of the graphene is protected; the annealing composite powder can improve the quality of graphene and improve the plastic deformation capacity of the composite powder; performing high-energy ball milling in a short time to weld the composite powder into particles without damaging the quality of graphene; in addition, for the composite material of the aluminum alloy matrix, the uniformly dispersed graphene promotes the precipitation of fine dispersed precipitated phases in the matrix, and the mechanical property of the composite material is further improved. The method is beneficial to protecting the structural integrity of the graphene to the maximum extent and exerting the reinforcing potential of the graphene, saves energy and time, and is suitable for batch preparation and production.
Description
Technical Field
The invention relates to the technical field of metal matrix composite materials, in particular to a powder metallurgy preparation method of a graphene reinforced aluminum matrix composite material.
Background
Aluminum and its alloys have been widely noticed due to their lower density, higher specific strength and specific modulus, and the aluminum alloys including pure aluminum, medium strength aluminum-magnesium-silicon system, high strength aluminum-copper system and ultra-high strength aluminum-zinc-magnesium-copper system are widely used in many fields such as aviation, aerospace, transportation, electronics, construction and sports goods, and the global production and usage of aluminum and its alloys are second only to that of steel materials. With the rapid development of the high-technology fields such as aerospace, national defense and military industry and the like, a single material is difficult to meet the use requirements of complex and harsh environments, the material is compounded into the development trend of the material, and a second phase with specific performance or excellent comprehensive performance is added into a Metal Matrix to form a Metal Matrix Composite (MMC) so as to make up for certain performance short plates of the Metal Matrix and realize the improvement of the comprehensive performance. A new-generation reinforcement represented by a nano-reinforcing phase such as graphene or carbon nanotube has been a focus of research in the field of composite materials in recent years. Compared with the ceramic brittle reinforcing phase in the traditional metal matrix composite material, the nano reinforcing phase (taking graphene as an example) has higher comprehensive performance, and is represented by high elastic modulus (1TPa), high tensile strength (130GPa), high tensile plasticity (more than 10%) and other mechanical properties and high conductivity (200,000 cm)2V-1s-1) High thermal conductivity (5000 Wm)-1K-1) On the functional characteristics, the characteristics of the nano reinforced phase-metal matrix composite system such as reinforcement, mold increasing efficiency, defect tolerance, tensile plasticity, electric conduction, heat conduction and the like are greatly improved compared with the traditional metal matrix composite, and the nano reinforced phase-metal matrix composite represents the future development direction of the metal matrix composite.
Due to the huge van der waals force existing between graphene layers, the uniform dispersion of graphene in a matrix is always a main obstacle for preparing the graphene reinforced aluminum-based composite material. The method of Molecular Level mixing (Molecular Level Mix), In Situ Synthesis (In Situ Synthesis), slurry blending sheet Powder Metallurgy (Flake Powder Metallurgy) and the like can better meet the requirement of exerting the uniform dispersion of graphene, but the method has relatively complex process and is difficult to carry out industrial production; in the graphene/aluminum-based composite material prepared by the traditional mechanical ball milling method, the dispersibility and the structural integrity of the nanophase are poorer, but the graphene/aluminum-based composite material is suitable for future large-scale and batch production and has certain industrial application potential. Therefore, how to develop a new graphene uniform dispersion technology in a mechanical ball milling method, keep the structure of the graphene uniform dispersion technology complete and well combine with a matrix, and the prepared composite material has no metallurgical defects, which is a key problem in the production and application technology of the existing graphene/aluminum-based composite material.
Through literature search of the prior art, the current research on the problem is mainly through ball milling-other processes combined with multi-step ball milling. Zheng et al ("Graphene nano-sheets re-expressed aluminum compositions with a non-aqueous composition" Materials Science&Engineering A798 (2020)140234) mixing aluminum powder and graphene by a ball milling method to obtain composite powder, preparing the composite material by multi-pass rolling after hot pressing to form an embryo, but the graphene reacts with a matrix to form brittle phase Al due to continuous high-temperature processing4C3The graphene nanostructure is seriously damaged, the strengthening effect is poor and the preparation process is complex; jiang et al ("decorating the structure and mechanical properties of graphene nano/aluminum compositions by floor powder mechanical shift-speed ball milling" compositions Part A111 (2018)73-82)After ball milling and mixing are carried out on the aluminum and graphene composite powder for 6h at 200rpm, ball milling is directly carried out on the aluminum and graphene composite powder for 0.5h at 500rpm, the mixed powder is continuously crushed and welded under the impact of steel balls in the ball milling process, finally, the graphene/aluminum spherical granular composite powder is formed, but the graphene nano structure is seriously damaged, and brittle phase Al is formed4C3The strengthening effect is not good. The disadvantages of the prior art are therefore mainly: the process cannot simultaneously meet the technical requirements of graphene dispersion, structural integrity, combination with a matrix and few metallurgical defects, so that the performance enhancement potential of graphene cannot be fully exerted in the metal matrix composite.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a powder metallurgy preparation method of a graphene reinforced aluminum matrix composite, which can be used for preparing a graphene/aluminum matrix composite on the premise of not damaging the structural integrity of graphene, so that the reinforcing effect of the graphene is fully exerted, and the graphene reinforced aluminum matrix composite with excellent mechanical property is obtained.
In order to achieve the above purpose, the invention provides a powder metallurgy preparation method of a graphene reinforced aluminum matrix composite, which comprises the steps of preparing graphene/aluminum composite powder by long-time low-energy ball milling in advance, annealing, and performing densification processes such as short-time high-energy ball milling, cold pressing, sintering/hot pressing, thermal deformation processing (forging/extruding/rolling) and the like and heat treatment (aiming at an aluminum alloy matrix composite) to finally obtain the high-performance graphene reinforced aluminum matrix composite. Because the deformation capacity of the spherical aluminum powder is limited, the residual stress of the long-time low-energy ball-milling aluminum/aluminum alloy powder is removed by adopting a stress-relief annealing process, the rapid rise (higher than 600 ℃) of the powder temperature caused by the ball-milling crushing of the direct high-energy ball-milling composite powder and the long-time high-energy ball-milling welding is avoided, the complete structure of the graphene is protected, and the generation of brittle phase Al is avoided4C3. Therefore, the method provided by the invention is beneficial to protecting the structural integrity of the graphene to the maximum extent, fully exerts the composite strengthening effect of the graphene, is energy-saving, time-saving, safe and feasible, and is suitable for batch preparation and production.
The purpose of the invention is realized by the following technical scheme:
the invention provides a powder metallurgy preparation method of a graphene reinforced aluminum-based composite material, which comprises the following steps:
a1, carrying out low-energy ball milling on the powder of graphene and an aluminum substrate to obtain uniformly mixed composite powder;
a2, performing stress relief annealing treatment on the composite powder;
a3, carrying out high-energy ball milling on the annealed composite powder to weld the composite powder, so as to obtain graphene/aluminum composite powder particles;
a4, carrying out densification processing on graphene/aluminum composite powder particles, and then carrying out heat treatment to obtain a graphene reinforced aluminum-based composite material;
the low-energy ball milling is as follows: the ball milling speed is 50-200 r/min, and the ball milling time is more than or equal to 6 hours;
the high-energy ball milling means that: the ball milling speed is 200-300 r/min, and the ball milling time is not more than 30 min.
Preferably, in the step A1, the aluminum substrate is aluminum or aluminum alloy, and the average particle diameter D50 of the spherical powder of the aluminum or aluminum alloy is between 10 and 100 μm.
Preferably, in step a1, the graphene includes one or more of graphene with a single-layer carbon structure, graphite oxide with a multi-layer carbon structure and derivatives thereof, and has a sheet diameter of less than 500nm and a thickness of less than 30 nm;
the mass percentage of the graphene in the graphene reinforced aluminum-based composite material is 0.1-5%, and the problems that the graphene is not uniformly dispersed, the composite material is difficult to compact and is easy to break and fail due to too high graphene content and the like can be caused.
Preferably, in the step a1, the low-energy ball milling is wet ball milling or dry ball milling; the high-energy ball milling is dry ball milling.
Preferably, when the low-energy ball milling is wet ball milling, the adopted solvent is selected from one of water, ethanol or kerosene; when the low-energy ball milling is dry ball milling, planetary ball milling or stirring ball milling is specifically adopted;
the dry ball milling adopted by the high-energy ball milling is planetary ball milling.
Preferably, when the dry ball milling is adopted, a process control agent is added in the process, and the process control agent is selected from one or more of methanol, ethanol, titanate, oleic acid, imidazoline or stearic acid.
Preferably, in step a4, the densification process specifically adopts any one or more of cold pressing, cold isostatic pressing, sintering, hot pressing, and hot deformation processes.
Preferably, the densification process is cold pressing or cold isostatic pressing; the sintering is any one of atmosphere sintering, vacuum hot pressing sintering, spark ion beam sintering or hot isostatic pressing sintering, and the sintering temperature is higher than the decomposition temperature of the ball-milling control agent but lower than the interface reaction temperature of graphene and aluminum.
Preferably, the hot deformation process includes one or more of hot forging, hot rolling, or hot extrusion.
Preferably, the annealing treatment of the composite powder is vacuum stress relief annealing, and the annealing temperature is the stress relief annealing temperature of the base material;
the heat treatment adopts aluminum alloy peak value aging treatment, the solid solution temperature is lower than the interface reaction temperature of graphene and aluminum, and the solid solution time is specifically determined by the precipitated phase melting time; the aging temperature is between 100 ℃ and 200 ℃, and the aging time is determined by the specific temperature and the alloy matrix.
The low-energy ball milling adopted by the invention has lower input energy, lower ball milling pressure and shearing force (the acting force of the milling balls on the powder can be decomposed into positive pressure and tangential shearing force), can gradually disperse graphene in the aluminum powder, does not obviously damage the graphene structure, and has poorer compactness of the composite powder prepared by the low-energy ball milling. The high-energy ball milling punching force and the shearing force are high, the input energy is high, the graphene cannot be fully dispersed under the action of the shearing force, the aluminum powder is rapidly flaked and is welded into particles by the high punching force, the powder is welded for multiple times to form compact granular composite powder, the cold welding impact force is far higher than the conventional powder metallurgy densification pressure, the metal in the particles is well combined with a reinforcement, and the defects of holes, microcracks and the like are few, so that the subsequent densification of the composite powder is facilitated; meanwhile, the granular composite powder has larger size and small specific surface area, so that the oxidation of the ball milling aluminum powder exposed in the air can be reduced, and the introduction of extra oxide inclusions is avoided, but the graphene is very easy to suffer from serious structural damage before being embedded into the aluminum powder granules, and the structural integrity of the graphene is not facilitated.
According to the technical scheme provided by the invention, firstly, the composite powder is gradually flaked under the action of pressure by utilizing the relatively long-time low-energy ball milling, the graphene is gradually dispersed on the surface of the flaked powder under the action of shearing force, then the hardening of the composite powder caused by the long-time ball milling is eliminated by stress relief annealing, and then the graphene/aluminum powder is subjected to cold welding granulation by the short-time high-energy ball milling. The loose volume of the granular composite powder is small, the micro defects needing to be closed in the process of preparing the block composite material by powder metallurgy processes such as green pressing, densification, deformation processing and the like of the granular composite powder are greatly reduced, the structural integrity of the graphene is effectively protected, and the potential of graphene compositing is fully exerted.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the graphene reinforced aluminum-based composite material prepared by the invention, graphene is uniformly dispersed, the structural integrity is well maintained, and no brittle phase Al exists4C3Generating;
(2) the composite material prepared by the invention has good graphene/aluminum matrix interface bonding and few metallurgical defects, and is beneficial to fully exerting the excellent reinforcing effect of graphene.
(3) The preparation method has the advantages of wide application range, energy and time conservation, reliable and efficient process and contribution to large-scale production.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic flow chart of a preferred embodiment of the present invention;
FIG. 2 is a scanning electron micrograph of a sample according to an embodiment of the present invention, wherein: FIG. 2(a) shows spherical aluminum powder; FIG. 2(b) is the surface of an aluminum sheet after long-term low-energy ball milling; FIG. 2(c) is a composite particle obtained after short time high energy ball milling; in fig. 2(b), the gray flakes are graphene;
FIG. 3 is a Raman spectroscopy spectrum of a sample in an example of the present invention, wherein: (a) graphene is taken as a raw material; (b) the composite powder is obtained after long-time low-energy ball milling; (c) the composite powder particles are obtained after short-time high-energy ball milling; (d) the final graphene reinforced aluminum matrix composite material is obtained;
FIG. 4 is a transmission electron micrograph of a sample in an example of the present invention, wherein: fig. 4(a) is a graphene distribution diagram, fig. 4(b) is a graphene-aluminum interface diagram, and the white arrows in fig. 4(a) indicate graphene.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
All the metal powders used in the following examples were spray-formed, and all the graphenes were graphite oxide, with a thickness of about 15nm and a sheet diameter of about 300 nm. All the examples were carried out according to the process shown in FIG. 1, and the room-temperature mechanical properties of the materials in all the examples were carried out according to GB/T228.1-2010, with a drawing rate of 0.18 mm/min.
Example 1
The present embodiment provides a preparation method of a graphene-reinforced aluminum-based composite material (containing 0.3 wt.% of graphene), as shown in fig. 1, the steps are as follows:
putting 49.85g of pure aluminum powder (spherical powder) with the particle size of 10 mu m and 0.15g of graphene in a stirring ball mill, taking ethanol as a solvent, adding 2g of phthalate coupling agent as a ball milling process control agent, taking stainless steel balls as a ball milling medium, carrying out ball milling for 10 hours at the rotating speed of 100 r/min at the ball-material ratio of 20:1 to obtain graphene/aluminum composite powder, carrying out suction filtration and drying, and carrying out vacuum annealing for 2 hours at the temperature of 200 ℃. FIG. 2(a) is an original spherical aluminum powder, and FIG. 2(b) is a graphene dispersion diagram of the surface of the aluminum sheet after stirring and ball milling for 10 h.
Placing the annealed graphene/aluminum composite powder in a planetary ball mill, adding 2g of stearic acid as a ball milling process control agent, under the protection of argon gas, taking a stainless steel ball as a ball milling medium, wherein the ball-material ratio is 20:1, and carrying out ball milling for 15min at a rotating speed of 200 revolutions per minute to obtain granular composite powder, wherein (c) in fig. 2 is a diagram of the composite granules after 15min high-energy ball milling.
The composite powder is sintered by hot isostatic pressing for 2h at 510 ℃ and 100MPa to prepare a blank with the diameter of 40mm, then the sintered blank is hot-stamped to a round cake with the thickness of about 10mm at 500 ℃, and the round cake is hot-rolled to a plate with the thickness of 2mm at 500 ℃, and the mechanical properties of the plate are listed in Table 1. FIG. 3 is a Raman spectrum (wherein (a) is graphene as a raw material, (b) is composite powder obtained after long-time low-energy ball milling, (c) is composite powder particles obtained after short-time high-energy ball milling, and (d) is a final graphene reinforced aluminum-based composite material).
Comparative example 1
This comparative example is essentially the same as example 1 except that: in this comparative example, no graphene was added. The method comprises the following specific steps:
taking 50g of spherical aluminum powder which is the same as that in the example 1, placing the spherical aluminum powder in a stirring ball mill, taking ethanol as a solvent, adding 2g of phthalate ester coupling agent as a ball milling process control agent, taking stainless steel balls as a ball milling medium, taking the ball-material ratio as 20:1, carrying out ball milling for 10 hours at the rotating speed of 100 r/min, and then carrying out vacuum annealing for 2 hours at the temperature of 200 ℃. Placing the annealed aluminum powder in a planetary ball mill, adding 2g of stearic acid as a ball milling process control agent, taking a stainless steel ball as a ball milling medium under the protection of argon gas, wherein the ball-material ratio is 20:1, and carrying out ball milling for 15min at the rotating speed of 200 r/min. The mechanical properties of the resulting base material, obtained by densifying and sintering aluminum powder and deforming the powder according to the same process as in example 1, are shown in table 1.
Example 2
The implementation provides a preparation method of a graphene-reinforced aluminum-based composite material (containing 0.6 wt.% of graphene), which comprises the following steps:
putting 49.7g of pure aluminum powder with the particle size of 10 mu m and 0.3g of graphene in a stirring ball mill, adding 2g of phthalate coupling agent serving as a ball milling process control agent by taking ethanol as a solvent, taking stainless steel balls as a ball milling medium with the ball-to-material ratio of 20:1, carrying out ball milling for 10 hours at the rotating speed of 100 r/min to obtain graphene/aluminum composite powder, carrying out suction filtration and drying, and carrying out vacuum annealing for 2 hours at the temperature of 200 ℃.
Placing the annealed graphene/aluminum composite powder in a planetary ball mill, adding 2g of stearic acid as a ball milling process control agent, taking a stainless steel ball as a ball milling medium under the protection of argon gas, wherein the ball-material ratio is 20:1, and carrying out ball milling for 15min at the rotating speed of 200 revolutions per minute to obtain the composite particles.
The composite powder is sintered by hot isostatic pressing for 2h at 510 ℃ and 100MPa to prepare a blank with the diameter of 40mm, then the sintered blank is hot-stamped to a round cake with the thickness of about 10mm at 500 ℃, and the round cake is hot-rolled to a plate with the thickness of 2mm at 500 ℃, and the mechanical properties of the plate are listed in Table 1.
Example 3
The implementation provides a preparation method of a graphene-reinforced aluminum-magnesium-silicon-based composite material (containing 0.4 wt.% of graphene), which comprises the following steps:
putting 49.8g of 6061 aluminum alloy powder with the particle size of 35 mu m and 0.2g of graphene in a planetary ball mill, adding 2g of stearic acid as a ball milling process control agent, under the protection of argon, taking stainless steel balls as a ball milling medium, ball milling for 6 hours at the rotating speed of 120 r/min at the ball-material ratio of 20:1 to obtain graphene/aluminum alloy composite powder, and carrying out vacuum annealing for 2 hours at the temperature of 200 ℃.
Placing the annealed graphene/aluminum alloy composite powder in a planetary ball mill, adding 2g of stearic acid as a ball milling process control agent, taking a stainless steel ball as a ball milling medium under the protection of argon gas, wherein the ball-material ratio is 20:1, and carrying out ball milling for 15min at the rotating speed of 250 revolutions/min to obtain the composite particles.
The composite powder is pre-sintered for 2 hours in a 510 ℃ vacuum sintering furnace after being cold-pressed into a blank, then the sintered blank is extruded into a round bar with the diameter of 8mm at the extrusion ratio of 16:1 and the extrusion speed of 1mm/min after being kept for 1 hour in a 350 ℃ vacuum extrusion furnace, and then the round bar is subjected to solid solution for 2 hours at 455 ℃ and aging for 4 hours at 175 ℃ to prepare the final graphene reinforced aluminum-magnesium-silicon alloy composite material, wherein the mechanical properties of the composite material are listed in Table 1. Fig. 4(a) is a transmission electron microscope image of graphene dispersion, and fig. 4(b) is a graphene-aluminum interface image.
Comparative example 2
This comparative example is essentially the same as example 3, except that: in this comparative example, no graphene was added. The method comprises the following specific steps:
50g of 6061 aluminum alloy powder which is the same as that in the embodiment 3 is taken and placed in a planetary ball mill, 2g of stearic acid is added as a ball milling process control agent, stainless steel balls are used as a ball milling medium under the protection of argon, the ball-material ratio is 20:1, ball milling is carried out for 6 hours at the rotating speed of 120 r/min, and then vacuum annealing is carried out for 2 hours at the temperature of 200 ℃. Placing the annealed aluminum alloy powder in a planetary ball mill, adding 2g of stearic acid as a ball milling process control agent, under the protection of argon, taking a stainless steel ball as a ball milling medium, wherein the ball-material ratio is 20:1, carrying out ball milling for 15min at a rotating speed of 250 revolutions per minute, carrying out densification and sintering, deformation processing and heat treatment on the alloy powder according to the same process in example 3, and finally obtaining the mechanical properties of the aluminum-magnesium-silicon alloy shown in Table 1.
Example 4
The present embodiment provides a method for preparing a graphene-reinforced aluminum-based composite material (containing 0.3 wt.% of graphene), which includes substantially the same steps as in example 1, except that:
when the graphene/aluminum composite powder is prepared, the ball milling speed is 50 revolutions per minute, and the ball milling time is 20 hours; when the granular composite powder is prepared, the ball milling rotating speed is 250 r/min, and the ball milling time is 10 min.
The mechanical properties of the final panels obtained are shown in table 1.
Example 5
The present embodiment provides a method for preparing a graphene-reinforced aluminum-based composite material (containing 0.3 wt.% of graphene), which includes substantially the same steps as in example 1, except that:
when the graphene/aluminum composite powder is prepared, the ball milling speed is 200 revolutions per minute, and the ball milling time is 6 hours; when the granular composite powder is prepared, the ball milling rotating speed is 300 r/min, and the ball milling time is 5 min.
The mechanical properties of the final panels obtained are shown in table 1.
Example 6
The embodiment provides a preparation method of a graphene-reinforced aluminum-based composite material (containing 0.1 wt.% of graphene), which comprises the following specific steps:
putting 49.95g of pure aluminum powder (spherical powder) with the particle size of 10 microns and 0.05g of graphene in a stirring ball mill, taking ethanol as a solvent, adding 2g of phthalate coupling agent as a ball milling process control agent, taking stainless steel balls as a ball milling medium, carrying out ball milling for 10 hours at the rotating speed of 100 revolutions per minute with the ball-material ratio of 20:1 to obtain graphene/aluminum composite powder, carrying out suction filtration and drying, and carrying out vacuum annealing for 2 hours at the temperature of 200 ℃.
Placing the annealed graphene/aluminum composite powder in a planetary ball mill, adding 2g of stearic acid as a ball milling process control agent, taking a stainless steel ball as a ball milling medium under the protection of argon gas, wherein the ball-material ratio is 20:1, and carrying out ball milling for 15min at a rotating speed of 200 revolutions per minute to obtain granular composite powder.
The composite powder is sintered by hot isostatic pressing for 2h at 510 ℃ and 100MPa to prepare a blank with the diameter of 40mm, then the sintered blank is hot-stamped to a round cake with the thickness of about 10mm at 500 ℃, and the round cake is hot-rolled to a plate with the thickness of 2mm at 500 ℃, and the mechanical properties of the plate are listed in Table 1.
Example 7
The embodiment provides a preparation method of a graphene-reinforced aluminum-based composite material (containing 1 wt.% of graphene), which comprises the following specific steps:
putting 49.5g of pure aluminum powder (spherical powder) with the particle size of 10 mu m and 0.5g of graphene in a stirring ball mill, taking ethanol as a solvent, adding 2g of phthalate coupling agent as a ball milling process control agent, taking stainless steel balls as a ball milling medium, carrying out ball milling for 10 hours at the rotating speed of 100 r/min at the ball-material ratio of 20:1 to obtain graphene/aluminum composite powder, carrying out suction filtration and drying, and carrying out vacuum annealing for 2 hours at the temperature of 200 ℃.
Placing the annealed graphene/aluminum composite powder in a planetary ball mill, adding 2g of stearic acid as a ball milling process control agent, taking a stainless steel ball as a ball milling medium under the protection of argon gas, wherein the ball-material ratio is 20:1, and carrying out ball milling for 15min at a rotating speed of 200 revolutions per minute to obtain granular composite powder.
The composite powder is sintered by hot isostatic pressing for 2h at 510 ℃ and 100MPa to prepare a blank with the diameter of 40mm, then the sintered blank is hot-stamped to a round cake with the thickness of about 10mm at 500 ℃, and the round cake is hot-rolled to a plate with the thickness of 2mm at 500 ℃, and the mechanical properties of the plate are listed in Table 1.
Example 8
The embodiment provides a preparation method of a graphene-reinforced aluminum-based composite material (containing 5 wt.% of graphene), which comprises the following specific steps:
putting 47.5g of pure aluminum powder (spherical powder) with the particle size of 10 mu m and 2.5g of graphene into a stirring ball mill, taking ethanol as a solvent, adding 2g of phthalate coupling agent as a ball milling process control agent, taking stainless steel balls as a ball milling medium, carrying out ball milling for 10 hours at the rotating speed of 100 r/min at the ball-material ratio of 20:1 to obtain graphene/aluminum composite powder, carrying out suction filtration and drying, and carrying out vacuum annealing for 2 hours at the temperature of 200 ℃.
Placing the annealed graphene/aluminum composite powder in a planetary ball mill, adding 2g of stearic acid as a ball milling process control agent, taking a stainless steel ball as a ball milling medium under the protection of argon gas, wherein the ball-material ratio is 20:1, and carrying out ball milling for 15min at a rotating speed of 200 revolutions per minute to obtain granular composite powder.
The composite powder is sintered by hot isostatic pressing for 2h at 510 ℃ and 100MPa to prepare a blank with the diameter of 40mm, then the sintered blank is hot-stamped to a round cake with the thickness of about 10mm at 500 ℃, and the round cake is hot-rolled to a plate with the thickness of 2mm at 500 ℃, and the mechanical properties of the plate are listed in Table 1.
Comparative example 3
The present comparative example provides a preparation method of a graphene-reinforced aluminum matrix composite (containing 0.3 wt.% of graphene), which has substantially the same specific steps as those of example 1, except that:
when the granular composite powder is prepared, the low-energy ball milling rotating speed is 150 r/min, and the ball milling time is 10 min.
The mechanical properties of the final panels obtained are shown in table 1.
Comparative example 4
The present comparative example provides a preparation method of a graphene-reinforced aluminum matrix composite (containing 0.3 wt.% of graphene), which has substantially the same specific steps as those of example 5, except that:
when the graphene/aluminum composite powder is prepared, the high-energy ball milling rotating speed is 250 revolutions per minute, and the ball milling time is 6 hours.
The mechanical properties of the final panels obtained are shown in table 1.
Comparative example 5
The present comparative example provides a preparation method of a graphene-reinforced aluminum matrix composite (containing 0.3 wt.% of graphene), which has substantially the same specific steps as those of example 5, except that:
and (2) when preparing the granular composite powder, performing wet ball milling, putting the annealed graphene/aluminum composite powder in a stirring ball mill, taking ethanol as a solvent, adding 2g of phthalate coupling agent as a ball milling process control agent, taking stainless steel balls as a ball milling medium, performing ball milling for 15min at a rotating speed of 200 revolutions per minute with a ball-to-material ratio of 20:1, and thus obtaining the graphene/aluminum composite powder.
The mechanical properties of the final panels obtained are shown in table 1.
TABLE 1 composition of composite materials, preparation method and mechanical properties at room temperature thereof
The raman spectrum analysis spectrums of the graphene reinforced aluminum matrix composite prepared by the above-listed embodiments are basically consistent, and the graphene dispersibility and the graphene/aluminum matrix interfacial bonding property are also basically consistent.
According to the powder metallurgy preparation method of the graphene reinforced aluminum-based composite material, provided by the invention, on the premise of uniformly dispersing graphene, the structural integrity of the graphene can be protected to the maximum extent, so that the reinforcing potential of the graphene is fully exerted, and the graphene reinforced aluminum-based composite material with excellent mechanical properties is obtained. The method is beneficial to exerting the effect of graphene composite reinforcement to the maximum extent, saves energy and time, is safe and easy to implement, and has the potential of large-scale application.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A powder metallurgy preparation method of a graphene reinforced aluminum matrix composite is characterized by comprising the following steps:
a1, carrying out low-energy ball milling on the powder of graphene and an aluminum substrate to obtain uniformly mixed composite powder;
a2, performing stress relief annealing treatment on the composite powder;
a3, carrying out high-energy ball milling on the annealed composite powder to weld the composite powder, so as to obtain graphene/aluminum composite powder particles;
a4, carrying out densification processing on graphene/aluminum composite powder particles, and then carrying out heat treatment to obtain a graphene reinforced aluminum-based composite material;
the low-energy ball milling is as follows: the ball milling speed is 50-200 r/min, and the ball milling time is more than or equal to 6 hours;
the high-energy ball milling means that: the ball milling speed is 200-300 r/min, and the ball milling time is not more than 30 min.
2. The powder metallurgy method for preparing graphene-reinforced aluminum-based composite material according to claim 1, wherein in the step A1, the aluminum substrate is aluminum or an aluminum alloy, and the average particle diameter D50 of the spherical powder of the aluminum or the aluminum alloy is 10-100 μm.
3. The powder metallurgy preparation method of graphene reinforced aluminum-based composite material according to claim 1, wherein in the step A1, the graphene comprises one or more of graphene with a single-layer carbon structure, graphite oxide with a multi-layer carbon structure and derivatives thereof, and has a sheet diameter of less than 500nm and a thickness of less than 30 nm;
the mass percentage of the graphene in the graphene reinforced aluminum-based composite material is 0.1-5%.
4. The powder metallurgy preparation method of graphene reinforced aluminum matrix composite according to claim 1, wherein in step a1, the low energy ball milling is wet ball milling or dry ball milling; the high-energy ball milling is dry ball milling.
5. The powder metallurgy preparation method of graphene reinforced aluminum matrix composite according to claim 4, wherein when the low energy ball milling is wet ball milling, the adopted solvent is one selected from water, ethanol or kerosene; when the low-energy ball milling is dry ball milling, planetary ball milling or stirring ball milling is specifically adopted;
the dry ball milling adopted by the high-energy ball milling is planetary ball milling.
6. The powder metallurgy preparation method of graphene reinforced aluminum-based composite material according to claim 4, wherein a process control agent is added in the dry ball milling process, and the process control agent is selected from one or more of methanol, ethanol, titanate, oleic acid, imidazoline or stearic acid.
7. The powder metallurgy preparation method of graphene reinforced aluminum-based composite material according to claim 1, wherein in the step A4, the densification processing is performed by any one or more of cold pressing, cold isostatic pressing, sintering, hot pressing and hot deformation processing.
8. The powder metallurgy preparation method of graphene reinforced aluminum matrix composite according to claim 6, wherein the densification process is cold pressing or cold isostatic pressing; the sintering is any one of atmosphere sintering, vacuum hot pressing sintering, spark ion beam sintering or hot isostatic pressing sintering, and the sintering temperature is higher than the decomposition temperature of the ball-milling control agent but lower than the interface reaction temperature of graphene and aluminum.
9. The powder metallurgy preparation method of graphene-reinforced aluminum-based composite according to any one of claim 6, wherein the hot deformation process comprises one or more of hot forging, hot rolling or hot extrusion.
10. The powder metallurgy preparation method of the graphene reinforced aluminum-based composite material according to claim 1, wherein the composite powder annealing treatment is vacuum stress relief annealing, and the annealing temperature is the stress relief annealing temperature of the matrix material;
the heat treatment adopts aluminum alloy peak value aging treatment, the solid solution temperature is lower than the interface reaction temperature of graphene and aluminum, and the solid solution time is specifically determined by the precipitated phase melting time; the aging temperature is between 100 ℃ and 200 ℃, and the aging time is determined by the specific temperature and the alloy matrix.
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